Porous Solids Research Articles

Correlative X-ray micro-nanotomography with scanning electron microscopy at the Advanced Light Source.

Geological samples are inherently multi-scale. Understanding their bulk physical and chemical properties requires characterization down to the nano-scale. A powerful technique to study the three-dimensional microstructure is X-ray tomography, but it lacks information about the chemistry of samples. To develop a methodology for measuring the multi-scale 3D microstructure of geological samples, correlative X-ray micro- and nanotomography were performed on two rocks followed by scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS) analysis. The study was performed in five steps: (i) micro X-ray tomography was performed on rock sample cores, (ii) samples for nanotomography were prepared using laser milling, (iii) nanotomography was performed on the milled sub-samples, (iv) samples were mounted and polished for SEM analysis and (v) SEM imaging and compositional mapping was performed on micro and nanotomography samples for complimentary information. Correlative study performed on samples of serpentine and basalt revealed multiscale 3D structures involving both solid mineral phases and pore networks. Significant differences in the volume fraction of pores and mineral phases were also observed dependent on the imaging spatial resolution employed. This highlights the necessity for the application of such a multiscale approach for the characterization of complex aggregates such as rocks. Information acquired from the chemical mapping of different phases was also helpful in segmentation of phases that did not exhibit significant contrast in X-ray imaging. Adoption of the protocol used in this study can be broadly applied to 3D imaging studies being performed at the Advanced Light Source and other user facilities.

Diels-Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes.

We investigated the Diels-Alder reaction of 6,13-bis(triisopropylsilyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off-center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring. Epoxynaphthalene adducts of 1 as well as its anthracene and tetracene congeners were deoxygenated, easily furnishing triarenobarrelenes with TIPS-ethynyl substituents at the bridge heads, attractive building blocks for porous solids and higher acene-based trimers.

Conversion of Carbon Dioxide into Molecular-based Porous Frameworks.

ConspectusThe conversion of carbon dioxide (CO2) to value-added functional materials is a major challenge in realizing a carbon-neutral society. Although CO2 is an attractive renewable carbon resource with high natural abundance, its chemical inertness has made the conversion of CO2 into materials with the desired structures and functionality difficult. Molecular-based porous materials, such as metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs), are designable porous solids constructed from molecular-based building units. While MOF/COFs attract wide attention as functional porous materials, the synthetic methods to convert CO2 into MOF/COFs have been unexplored due to the lack of synthetic guidelines for converting CO2 into molecular-based building units.In this Account, we describe state-of-the-art studies on the conversion of CO2 into MOF/COFs. First, we outline the key design principles of CO2-derived molecular building units for the construction of porous structures. The appropriate design of reactivity and the positioning of bridging sites in CO2-derived molecular building units is essential for constructing CO2-derived MOF/COFs with desired structures and properties. The synthesis of CO2-derived MOF/COFs involves both the transformation of CO2 into building units and the formation of extended structures of the MOF/COFs. We categorized the synthetic methods into three types as follows: a one-step synthesis (Type-I); a one-pot synthesis without workup (Type-II); and a multistep synthesis which needs workup (Type-III).We demonstrate that borohydride can convert CO2 into formate and formylhydroborate that serve as a bridging linker for MOFs in the Type-I and Type-II synthesis, representing the first examples of CO2-derived MOFs. The electronegativity of coexisting metal ions determines the selective conversion of CO2 into formate and formylhydroborate. Formylhydroborate-based MOFs exhibit flexible pore sizes controlled by the pressure of CO2 during synthesis. In pursuit of highly porous structures, we present the Type-I synthesis of MOFs from CO2 via the in situ transformation of CO2 into carbamate linkers by amines. The direct conversion of diluted CO2 (400 ppm) in air into carbamate-based MOFs is also feasible. Coordination interactions stabilize the intrinsically labile carbamate in the MOF lattice. A recent study demonstrates that the Type-III synthesis using alkynylsilane precursors enables the synthesis of highly porous and stable carboxylate-based MOFs from CO2, which exhibit catalytic activity in CO2 conversion. We also extended the synthesis of MOFs from CO2 to COFs. The Type-III synthesis using a formamide monomer affords stable CO2-derived COFs showing proton conduction properties. The precise design of CO2-derived building units enables expansion of the structures and functionalities of CO2-derived MOF/COFs. Finally, we propose future challenges in this field: (i) expanding structural diversity through synthesis using external fields and (ii) exploring unique functionalities of CO2-derived MOF/COFs, such as carriers for CO2 capture and precursors for CO2 transformation. We anticipate that this Account will lay the foundation for exploring new chemistry of the conversion of CO2 into porous materials.

Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks.

Transformation between oxidation states is widespread in transition metal coordination chemistry and biochemistry, typically occurring in solution. However, air-induced oxidation in porous crystalline solids with retention of crystallinity is rare due to the dearth of materials with high structural stability that are inherently redox active. Herein, we report a new family of such materials, four isostructural cobalt-pyrazolate frameworks of face-centered cubic, fcu, topology, fcu-L-Co, that are sustained by Co8 molecular building blocks (MBBs) and dipyrazolate ligands, L. fcu-L-Co were observed to spontaneously transform from Co(II)8 to Co(III)8 MBBs in air with retention of crystallinity, marking the first such instance in metal-organic frameworks (MOFs). This transformation can also be achieved through water vapor sorption cycling, heating, or chemical oxidation. The reverse reactions were conducted by exposure of fcu-L-Co(III) to aqueous hydrazine. fcu-L-Co(II) exhibited high gravimetric water vapor uptakes of 0.55-0.68 g g-1 at 30% relative humidity (RH), while in fcu-L-Co(III) the inflection point shifted to lower RH and framework stability improved. Insight into the transformation between fcu-L-Co(II) and fcu-L-Co(III) was gained from single crystal X-ray diffraction and in situ spectroscopy. Overall, the crystal engineering approach we adopted has afforded a new family of MOFs that exhibit cobalt redox chemistry in a confined space coupled with high porosity.

Analytic solutions for effective elastic moduli of isotropic solids containing oblate spheroid pores with critical porosity

AbstractAccurate characterization for effective elastic moduli of porous solids is crucial for better understanding their mechanical behaviour and wave propagation, which has found many applications in the fields of engineering, rock physics and exploration geophysics. We choose the spheroids with different aspect ratios to describe the various pore geometries in porous solids. The approximate equations for compressibility and shear compliance of spheroid pores and differential effective medium theory constrained by critical porosity are used to derive the asymptotic solutions for effective elastic moduli of the solids containing randomly oriented spheroids. The critical porosity in the new asymptotic solutions can be flexibly adjusted according to the elastic moduli – porosity relation of a real solid, thus extending the application of classic David‐Zimmerman model because it simply assumes the critical porosity is one. The asymptotic solutions are valid for the solids containing crack‐like oblate spheroids with aspect ratio < 0.3, nearly spherical pores (0.7 < < 1.3) and needle‐like prolate pores with > 3, instead of just valid in the limiting cases, for example perfectly spherical pores (= 1) and infinite thin cracks (0). The modelling results also show that the accuracies of asymptotic solutions are weakly affected by the critical porosity and grain Poisson's ratio , although the elastic moduli have appreciable dependency of and . We then use the approximate equations for pore compressibility and shear compliance as inputs into the Mori–Tanaka and Kuster–Toksoz theories and compare their calculations to our results from differential effective medium theory. By comparing the published laboratory measurements with modelled results, we validate our asymptotic solutions for effective elastic moduli.

Integration of deep eutectic solvent with adsorption and membrane-based processes for CO2 capture: An innovative approach

CO2 capture strategies have been implemented to address climate change by reducing CO2 emissions from large-scale sources such as fossil fuel power plants and natural gas upgrading. Deep eutectic solvents (DESs) are a new class of green solvents with good CO2 affinity, simple synthesis steps, inexpensive raw materials, non-toxic and non-volatile properties. For these reasons, they are a promising platform for CO2 capture applications and have tremendous untapped potential to enhance the performance of the adsorption and membrane-based separation processes. Unlike existing reviews which have focused on the functionalities of DESs, as well as the physicochemical and CO2 solubility properties of DESs, this mini-review discusses the integration of DESs with adsorption and membrane processes to evaluate their CO2 separation performance. Moreover, simulation and computational studies on DES-based systems, including confinement in porous solids and membranes, are discussed. Finally, perspectives on developing DES-based adsorbents and DES-based membranes for the CO2 separation field are presented. This review provides insight into the potential of integrating DESs with CO2 capture technologies to enhance the performance of hybrid systems in relation to standalone approaches.

Influential mechanism of water occurrence states of waste-activated sludge: Specifically focusing on the pore characteristics dominated by cation-organic interactions

The solid pore characteristics are commonly considered as the important influential factors on waste-activated sludge (WAS) dewaterability, and should be related to the cohesive force of bio-flocs dominated by cation-organic interactions at solid-water interface. This study aimed to establish an approach for regulating the solid pore structure of WAS by cationic regulation. The influential mechanism of WAS dewaterability was accordingly explored from the perspective of the pore characteristics dominated by cation-organic interactions. Primarily, with the gradient removal or addition of bivalent cations, the varying pore structure of WAS flocs was tracked by in-situ synchrotron X-ray computed microtomography imaging technique (CMT). The three-dimensional visual model was established to quantify the pore structure parameters of WAS flocs. Following the visualization analysis, the artificial intelligence means, the gradient-weighted class activation mapping (Grad CAM) of three-dimensional convolutional neural network (3D-CNN), was applied for the first time to explore the linkages among solid surface properties, solid pore structure, water occurrence states and sludge dewaterability. It was found that the number and volume of isolated pores jointly determined the mobility and the fractions of vicinal water and interstitial water (p-value ≤ 0.02); also, the decreasing polar or acid-based interfacial free energy with the cationic addition was accompanied with the decreasing isolated pore mean-volume (Pearson coefficient=-0.77, p-value < 0.01). These results indicated that the pore structure characteristics determined the water occurrence states, but the solid porosity strongly depended on the interfacial properties. Accordingly, the molecular docking was applied to explore the interfacial reaction mechanism between Ca2+/Mg2+ and solid compositions in terms of complexation sites, molecular dynamics and free energy calculations. As a result, how the cation-organic interactions affected the pore characteristics through solid surface modification could be clarified, which is expected to serve as theoretical foundation for the development of novel sludge conditioning technologies, i.e., more efforts should be devoted to increasing the dense degree of sludge particles through weakening the hydration repulsion of solid surface.

Combined effects of pores and cracks on the effective thermal conductivity of materials: a numerical study

Porous solids are commonplace in engineering structures and in nature. Material properties are inevitably affected by the internal inhomogeneity. The effective thermal conductivity of porous materials has been and remains to be a subject of extensive research. Less attention has been devoted to thermal conductivity impacted by internal cracks. This study is devoted to theoretical analyses of the combined effects of pores and cracks on the effective thermal conductivity. Systematic numerical simulations using the finite element method are performed based on two-dimensional models, with periodic distributions of internal pores and cracks. The parametric investigations seek to address how individual geometric layout can influence the overall thermal conduction behavior. In addition to circular pores and isolated cracks, angular pores with cracks extending from their sharp corners are also considered. It is found that both isolated cracks and cracks connected to existing pores can significantly reduce the effective thermal conductivity in porous materials. Since it is much easier to microscopically detect internal pores than thin cracks, care should be taken in using the apparent porosity from microscopic images and density measurements to estimate the overall thermal conductivity. Quantitative analyses of the detailed geometric effects are reported in this paper.

New technology research of efficient utilization of geothermal energy

Abstract Geothermal energy is being widely valued as a clean energy source. Underground structure has a controlling influence on the geothermal development. If the underground structure can be visualized, it is the key technology to improve the geothermal development. Through the streaming potential detection technology, under the action of external pressure, the liquid can be forced to flow through the solid pores to generate directional flow, and the flow potential can be generated at both ends of the solid pores. Different streaming potential phenomena under pressure can help engineer to distinguish different geological structures. A set of laboratory tests was designed to prove the feasibility and accuracy of this proposed detection methods, and tests were conducted using the core injection system and the streaming potential tester to carry out injection on sandstone specimens of two different structures, to study the effect of different injection pressures and different salinity on variation of streaming potential in sandstone. The laboratory test results show that the flow potential is accompanied by the liquid injection process in the sandstone specimen, and the flow potential produced by the sandstone with different porosity is obviously different, so the flow potential accompanying the actual rock injection process can be used to distinguish different geological structures, and this study provides a new idea for studying geological structures, and are expected to improve the efficiency of geothermal development.

Mechanical characteristics and constitutive model of cemented tailings backfill under temperature-time effects

The increase in original rock temperature during the deep metal mine backfill mining process significantly impacts the mechanical properties of cemented tailings backfill (CTB). Uniaxial compression experiments were conducted under various curing temperatures and times, analyzing their mechanical characteristics based on strain energy. The experimental results indicate that the mechanical properties of CTB are significantly affected by temperature. The uniaxial compressive strength (UCS) follows a quadratic trend, initially increasing and then decreasing as the curing temperature changes. At the curing temperature of 40 °C, the hydration reaction of CTB develops fully, the hydration products have strong compactness, and the energy absorbed when failure occurs is the largest. The CTB is divided into a solid framework and pore sections to develop a constitutive damage model using a combined macro and micro experimental approach. Polynomial functions represent the correlation between the damage model parameters and curing time and temperature, resulting in a unified temperature-time damage constitutive model. Using the secondary development platform in FLAC3D finite difference software, the damage constitutive model of the CTB was further developed and integrated into the software, enabling both its development and application. This customized model provides a more comprehensive representation of the overall deformation and failure mechanisms of the CTB during compression. The study can predict the strength of CTB under different curing conditions, and provide theoretical reference for the simulation research of filling mining in mines.

Experimental and computational aspects of molecular frustrated Lewis pairs for CO2 hydrogenation: en route for heterogeneous systems?

Catalysis plays a crucial role in advancing sustainability. The unique reactivity of frustrated Lewis pairs (FLPs) is driving an ever-growing interest in the transition metal-free transformation of small molecules like CO2 into valuable products. In this area, there is a recent growing incentive to heterogenize molecular FLPs into porous solids, merging the benefits of homogeneous and heterogeneous catalysis - high activity, selectivity, and recyclability. Despite the progress, challenges remain in preventing deactivation, poisoning, and simplifying catalyst-product separation. This review explores the expanding field of FLPs in catalysis, covering existing molecular FLPs for CO2 hydrogenation and recent efforts to design heterogeneous porous systems from both experimental and theoretical perspectives. Section 2 discusses experimental examples of CO2 hydrogenation by molecular FLPs, starting with stoichiometric reactions and advancing to catalytic ones. It then examines attempts to immobilize FLPs in porous matrices, including siliceous solids, metal-organic frameworks (MOFs), covalent organic frameworks, and disordered polymers, highlighting current limitations and challenges. Section 3 then reviews computational studies on the mechanistic details of CO2 hydrogenation, focusing on H2 splitting and hydride/proton transfer steps, summarizing efforts to establish structure-activity relationships. It also covers the computational aspects on grafting FLPs inside MOFs. Finally, Section 4 summarizes the main design principles established so far, while addressing the complexities of translating computational approaches into the experimental realm, particularly in heterogeneous systems. This section underscores the need to strengthen the dialogue between theoretical and experimental approaches in this field.

Fluid transport in Ordinary Portland cement and slag cement from in-situ positron emission tomography

Fluid transport in cementitious matrices and materials is fundamental for many engineering and environmental applications. However, observing and measuring transport processes inside opaque porous solids, such as cement, is technically challenging. We tested the feasibility of using Positron Emission Tomography (PET) for in-situ tracking of fluid being spontaneously imbibed into cementitious matrices. We found that the 124I radiotracer enables tracking of the 3D spatiotemporal distribution of the fluids moving through the solid phase. Our measurements show a similar transport rate for Ordinary Portland (CEM І) and slag (CEM ІІІ/B) cement pastes. For both cement types, we found that the fluid penetration depth is proportional to t0.25. Such a relationship indicates anomalous transport and agrees with standard imbibition/sorptivity experiments. This result confirms that the method offers a reliable technique to explore transport phenomena in cementitious materials.

A Novel Approach to Continuum FE Multiphysics Simulation of Batteries via Heterogeneous Homogenization

Advancements in modern technology necessitate batteries that can be safely charged and discharged at high rates with minimal aging. A promising strategy to achieve these ends is through optimization of porous microstructures of existing electrode materials to promote better electrical and ionic transport without compromising energy density, as has been shown experimentally by introducing laser ablation channels to the electrodes. The present work proposes a microstructure up-scaling methodology that efficiently accounts for material heterogeneity by assigning a porosity field to a continuum scale finite element mesh, effectively homogenizing materials while maintaining the heterogeneous porosity distribution inherent to the original microstructure. Constitutive relationships relating solid electric conductivity and pore tortuosity to local porosity are directly computed from fully resolved anode, cathode, and separator microstructure 3D models and assigned in the continuum as material properties of a finite element mesh. This allows for utilization of the computationally efficient, homogenized Newman model while maintaining dependency on the heterogeneous local porosity. Then, coupled electrochemical-thermal-mechanical-pore pressure finite element simulations are performed on the battery cell model with this heterogeneous porosity field, and associated local variations on transport properties are prescribed as material properties by the precomputed constitutive relationships. Performance metrics and lithium plating potential are compared to the results of simulations of the fully homogenized cell with the same constitutive relationships and to the base case of a fully homogenous cell with typical modelling assumptions applied to porosity dependent constitutive relationships. These comparisons are made both as a means of validating the methodology and to demonstrate the vast differences that arise when simplifying assumptions are used instead of the constitutive relationships of the actual material microstructure. Finally, the methodology is used in its intended optimization application to compare the performance of a typical battery microstructure to a similar porous microstructure with micro holes added via laser ablation. The results indicate that differences in the microstructure of materials with identical average porosities and similar constitutive relationships can have significant differences in both cell performance and aging that would typically be impossible to detect using fully homogeneous continuum modeling. Figure 1

Stress Analysis of a Concrete Pipeline in a Semi-Infinite Seabed under the Action of Elliptical Cosine Waves Based on the Seepage Equation

This study aims to investigate the mechanical response of a submarine concrete pipeline under wave action in shallow waters, taking into account factors such as the compressibility of pores and the permeability of the seabed. The control equation of the elliptical cosine wave theory is adopted to simulate the action of waves. In order to simulate the interaction between the solid skeleton and pore fluid, the concept of a “porous medium” is used to establish the transient seepage control equation. Utilizing the stress and displacement conditions at the interface of the ideal fluid media, porous media, and concrete pipeline, the numerical solutions for the internal force and pore pressure of the concrete pipeline buried in a semi-infinite thickness seabed were obtained; meanwhile, the effects of changes in the gas content in pore water and changes in the seabed permeability coefficient on a concrete pipeline were analyzed. The numerical calculation results show that, with the increase in the gas content in the pore water, the amplitude of the pore pressure on the pipeline surface decreases, and both the horizontal and vertical forces acting on the pipeline decrease; the amplitude of the pore pressure on the pipeline surface increases with the increase in seabed permeability and decreases with the enhancement of seabed permeability anisotropy; the improvement of the seabed permeability or enhancement of the permeability anisotropy can increase the horizontal force acting on the pipeline. This study provides a reference for the stability evaluation of submarine concrete pipelines under wave action in shallow water areas.

Geometric Tuning of Coordinatively Unsaturated Copper(I) Sites in Metal-Organic Frameworks for Ambient-Temperature Hydrogen Storage.

Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H2 adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H2 interactions for ambient-temperature storage. Recently, Cu2.2Zn2.8Cl1.8(btdd)3 (H2btdd = bis(1H-1,2,3-triazolo-[4,5-b],[4',5'-i])dibenzo[1,4]dioxin; CuI-MFU-4l) was reported to show a large H2 adsorption enthalpy of -32 kJ/mol owing to π-backbonding from CuI to H2, exceeding the optimal binding strength for ambient-temperature storage (-15 to -25 kJ/mol). Toward realizing optimal H2 binding, we sought to modulate the π-backbonding interactions by tuning the pyramidal geometry of the trigonal CuI sites. A series of isostructural frameworks, Cu2.7M2.3X1.3(btdd)3 (M = Mn, Cd; X = Cl, I; CuIM-MFU-4l), was synthesized through postsynthetic modification of the corresponding materials M5X4(btdd)3 (M = Mn, Cd; X = CH3CO2, I). This strategy adjusts the H2 adsorption enthalpy at the CuI sites according to the ionic radius of the central metal ion of the pentanuclear cluster node, leading to -33 kJ/mol for M = ZnII (0.74 Å), -27 kJ/mol for M = MnII (0.83 Å), and -23 kJ/mol for M = CdII (0.95 Å). Thus, CuICd-MFU-4l provides a second, more stable example of optimal H2 binding energy for ambient-temperature storage among reported metal-organic frameworks. Structural, computational, and spectroscopic studies indicate that a larger central metal planarizes trigonal CuI sites, weakening the π-backbonding to H2.

Tensile deformation and failure of AlSi10Mg random cellular metamaterials

Cellular metamaterials are an emerging class of porous materials, in which the topology of the solid is precisely-engineered to achieve attractive combinations of properties. This work specifically examines the tensile response of a novel type of cellular metamaterials, in which pores of arbitrary elliptical shape are randomly-dispersed into an aluminum alloy matrix. Their porous mesostructure is generated numerically via a random sequential absorption algorithm, and is fabricated by laser powder bed fusion from AlSi10Mg powders. The results – obtained by means of digital image correlation combined with X-ray tomography – highlight the advantages offered by a random cellular topology. They are notably a low sensitivity to geometric imperfections (which inevitably result from manufacturing), coupled with the ability to delay long-wavelength strain localization, which is in turn responsible for failure. Structural disorder also leads to highly heterogeneous deformation patterns, which result from the interaction between geometric pores and promote void growth and coalescence during plastic straining. The presence of manufacturing defects exacerbates void interaction and promotes early plastic flow localization. Interestingly, experiments reveal that this class of porous solids effectively displays features of the ductile fracture of metals at the mesoscale. For example, void-sheeting is observed with increasing pore aspect ratio and is accompanied by large geometric distortions of the voids upon coalescence. Measured data for the pore strains are highly scattered and show a departure from McClintock’s model predictions for the voids within the fracture band. Collectively, this study highlights the potential offered by random porous metamaterials, which can be harnessed to revisit the complex mechanisms of ductile fracture at the mesoscale.

Reconstruction and Generation of Porous Metamaterial Units via Variational Graph Autoencoder and Large Language Model

Abstract In this paper, we propose and compare two novel deep generative model-based approaches for the design representation, reconstruction, and generation of porous metamaterials characterized by complex and fully connected solid and pore networks. A highly diverse porous metamaterial database is curated, with each sample represented by solid and pore phase graphs and a voxel image. All metamaterial samples adhere to the requirement of complete connectivity in both pore and solid phases. The first approach employs a Dual Decoder Variational Graph Autoencoder to generate both solid phase and pore phase graphs. The second approach employs a Variational Graph Autoencoder for reconstructing/generating the nodes in the solid phase and pore phase graphs and a Transformer-based Large Language Model (LLM) for reconstructing/generating the connections, i.e., the edges among the nodes. A comparative study is conducted, and we found that both approaches achieved high accuracy in reconstructing node features, while the LLM exhibited superior performance in reconstructing edge features. Reconstruction accuracy is also validated by voxel-to-voxel comparison between the reconstructions and the original images in the test set. Additionally, discussions on the advantages and limitations of using LLMs in metamaterial design generation, along with the rationale behind their utilization, are provided.

Molecular dynamics study on the diffusion of organosulfur compounds in porous solids

Molecular dynamics study on the diffusion of organosulfur compounds in porous solids

Shale pore characteristics and their impact on the gas-bearing properties of the Longmaxi Formation in the Luzhou area

Deep shale has the characteristics of large burial depth, rapid changes in reservoir properties, complex pore types and structures, and unstable production. The whole-rock X-ray diffraction (XRD) analysis, reservoir physical property parameter testing, scanning electron microscopy (SEM) analysis, high-pressure mercury intrusion testing, CO2 adsorption experimentation, and low-temperature nitrogen adsorption–desorption testing were performed to study the pore structure characteristics of marine shale reservoirs in the southern Sichuan Basin. The results show that the deep shale of the Wufeng Formation Longyi1 sub-member in the Luzhou area is superior to that of the Weiyuan area in terms of factors controlling shale gas enrichment, such as organic matter abundance, physical properties, gas-bearing properties, and shale reservoir thickness. SEM is utilized to identify six types of pores (mainly organic matter pores). The porosities of the pyrobitumen pores reach 21.04–31.65%, while the porosities of the solid kerogen pores, siliceous mineral dissolution pores, and carbonate dissolution pores are low at 0.48–1.80%. The pores of shale reservoirs are mainly micropores and mesopores, with a small amount of macropores. The total pore volume ranges from 22.0 to 36.40 μL/g, with an average of 27.46 μL/g, the total pore specific surface area ranges from 34.27 to 50.39 m2/g, with an average of 41.12 m2/g. The pore volume and specific surface area of deep shale gas are positively correlated with TOC content, siliceous minerals, and clay minerals. The key period for shale gas enrichment, which matches the evolution process of shale hydrocarbon generation, reservoir capacity, and direct and indirect cap rocks, is from the Middle to Late Triassic to the present. Areas with late structural uplift, small uplift amplitude, and high formation pressure coefficient characteristics favor preserving shale gas with high gas content and production levels.

Nanoparticle shape factor impact on double diffusive convection of Cu-water nanofluid in trapezoidal porous enclosures: A numerical study

Enclosures that contain both fluid and porous regions are utilized in various industries and geophysical processes to enhance heat and mass transfer. These enclosures find applications in fields such as geothermal engineering, drying of porous solids, cooling of electronics, metal solidification, and many others. In line with the motivation behind these applications, the present study explores double diffusion in the naturally convective flow of water-based nano fluid saturated in the trapezoidal porous enclosure and containing Copper (Cu) nano particles. The impact of uniformly applied radiative heat flux and nano particle shape factor is also accounted. A numerical investigation was carried out using a finite difference methodology integrated into a computational MATLAB code for numerical simulation. The simulation aimed to study the effect of nanoparticle shape factor on the effectiveness of a porous medium, which is exposed to two distinct objectives: enhancing heat transfer and optimizing mass transfer within a fluid-saturated porous medium. This research conducts a meticulous parametric exploration, underscoring the pivotal roles played by Darcy number (Da), nanofluid shape factor (m), Rayleigh number (Ra), thermal radiation (Rd), buoyancy ratio (Nr), and Lewis number (Le) in shaping the dynamics of flow, heat, and concentration transfer. The analysis of Nusselt and Sherwood numbers reveals that changing the shape of nano-particles from spheres to bricks increases the heat flux and mass flux coefficients by approximately 0.33% and 1.37% respectively. The results show a significant increase in Nusselt and Sherwood numbers, with blade-shaped nanoparticles demonstrating approximately a 2.97% and 10.82% improvement, respectively, compared to sphere-shaped nanoparticles. The outcome of this analysis yields an exhaustive dataset encompassing Nusselt and Sherwood numbers can be written as mathematical functions based on the parameters we talked about earlier.